Catalytic film polymerization of acetylene

ABSTRACT

An apparatus for producing a polyacetylene film by contacting acetylene gas with Ziegler-Natta catalyst to polymerize the acetylene gas in a vessel which comprises a catalyst introduction conduit to be introduced with the Ziegler-Natta catalyst provided at a cap provided at the top of the vessel and having an end opening disposed in the vicinity of the inner surface of the side wall of the vessel in such a manner that the conduit and the vessel are relatively moved in rotation, and a rotary transmission mechanism for driving to rotatably coat the catalyst flowed out from the end opening of the conduit on the inner surface of the bottom from the inner surface of the side wall of the vessel. Thus, the polyacetylene film can be produced in a uniform thickness and in a relatively large area by introducing the Ziegler-Natta catalyst of the suitable quantity, and the catalyst can be spread over the entire surface rapidly by the relative rotation between the conduit and the vessel.

This is a division of application Ser. No. 649,506 filed Sept. 11, 1984now U.S. Pat. No. 4,663,123.

BACKGROUND OF THE INVENTION

This invention relates to an apparatus for producing a polyacetylenefilm and, more particularly, to such an apparatus adapted to produce apolyacetylene film having uniform thickness and large area.

A polyacetylene is the most simple chain conjugated high-molecularcompound which contains as ingredients a carbon atom and a hydrogenatom, and has properties as a semiconductor. Particularly, apolyacetylene membrane which is laminated with Ziegler-Natta catalyst(Ti(OC₄ H₉)₄ -Al(C₂ H₅)₃ series ) has fibril (fibrous ultrafine crystal)mesh structure of approx. 200 Å in diameter. When this membrane isslightly doped with halogen gas or arsenic pentafluride, itsconductivity can be largely varied.

Since such a polyacetylene membrane has extreme chemical stability, alight weight and a fibril mesh structure, resulting in a large surfacearea, the polyacetylene membrane has already been noted as a favorableelectrode material for a secondary battery in applications to integratedcircuits.

As a method of producing the above-described polyacetylene film, it washeretofore known to produce the polyacetylene film by the method whichhas the steps of preparing the molar ratio of aluminum/titanium of theZiegler-Natta catalyst to 3 to 4, and cooling the catalyst at -78° C.with a refrigerant of a dry ice methanol, blowing acetylene gas onto thecatalyst, thereby polymerizing the gas in the vicinity of the boundarybetween the vapor phase and the liquid phase in the surface of thecatalyst solution.

An apparatus of the prior art is illustrated in FIG. 1.

In order to heretofore produce actually the above-describedpolyacetylene film, Ziegler-Natta b is stored in a cylindrical vessel a,the vessel a is fluctuated to adhere the catalyst b to the inner wallsurface a' of the vessel a, acetylene gas is introduced from the supplytube c into the vessel a, thereby forming a polyacetylene film dobtained by the polymerization of the gas over the boundary between thevapor phase and the liquid phase of the catalyst b stored in the bottomof the vessel a from the catalyst b adhered to the inner wall surfacea'.

In the conventional case, the polyacetylene film d produced on thesurface b' in the catalyst b in the bottom is impregnated with a largequantity of catalyst in the fibril mesh structure. Accordingly, itsquality is deteriorated, thus only the polyacetylene film d produced onthe inner wall surface a' can be utilized as the material for theelectrode of the secondary battery or the other field. The productionefficiently is therefore low. Further the catalyst b adhered to theperipheral surface a' tends to flow down toward the bottom surface evenin the polyacetylene film d of the inner wall surface. Thus, the bottomside becomes too thick, resulting in an irregular thickness. Further, itis difficult to adhere the catalyst sufficiently to the upper part ofthe surface a'. Thus, it is necessary to store a large quantity of thecatalyst in the bottom and to rotate it at a high speed, therebydisadvantageously causing the film of high quality not to be produced.

SUMMARY OF THE INVENTION

Accordingly, it is an object of this invention to provide an apparatusfor producing a polyacetylene film which can eliminate theaforementioned drawbacks and disadvantages, which can continuouslyfreely coat catalyst from the inner surface of the side wall to theinner surface of the bottom of a container by arranging a catalystintroduction conduit for coating the catalyst on the inner surface ofthe side wall of the container and rotatably move the container and theconduit relative to each other to produce a uniform polyacetylene film,thereby eliminating the problems described above.

It is another object of this invention to provide an apparatus forproducing a polyacetylene film which can, in addition to the aboveobject, continuously freely coat catalyst from the inner surface of theside wall to the inner surface of the bottom of the container by formingthe bottom of the container in a tapered shape, having an outlet and torotatably move the container and a catalyst introduction conduitrelative to each other to produce a uniform polyacetylene film, therebyfurther improving the advantages of the above object.

The above and other related objects and features of the invention willbe apparent from a reading of the following description of thedisclosure found in the accompanying drawings and the novelty thereofpointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic vertical sectional front view showing aconventional apparatus for producing a polyacetylene film;

FIGS. 2 and 3 are vertical sectional front and plan views of anembodiment of an apparatus for producing a polyacetylene film accordingto the present invention;

FIGS. 4 and 5 are vertical sectional front and plan views of anotherembodiment of an apparatus for producing a polyacetylene film accordingto the present invention;

FIGS. 6 and 7 are vertical sectional front and plan views of stillanother embodiment of an apparatus for producing a polyacetylene filmaccording to the present invention;

FIGS. 8 and 9 are vertical sectional front and plan views of stillanother embodiment of an apparatus for producing a polyacetylene filmaccording to the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described in more detail withreference to the accompanying drawings.

In FIGS. 2 and 3, reference numeral 1 designates a vessel formed in acovered cylindrical shape. An opening is formed at the center of aceiling wall 1c of the vessel 1. The vessel 1 is slidably contacted withan O-ring 3 engaged with the outer periphery of the lower end of acup-shaped cap 4 at the upper end face of the peripheral edge of theopening 2. The cap 4 is fixedly secured by fastening arm levers 5. Thevessel 1 is rotatably supported to a rotatable support shaft 1' as anaxial center.

A conduit 6 for introducing acetylene gas, connected to a supply source,not shown, and an exhaust conduit 7 for flowing the acetylene gas in thevessel 1 out are opened and passed through the vessel 1 at the cap 4,and control valves 8, 9 are respectively provided at the conduits 6 and7 for maintaining the acetylene gas atmosphere under a predeterminedconstant pressure.

Further, a conduit 10 connected to the supply source, not shown, forintroducing catalyst such as Ziegler-Natta catalyst, is passed throughthe cap 4, and the conduit 10 of the part extended into the vessel 1 isbent substantially in L shape. The opening 10a at the end of the conduit10 is disposed in the vicinity of the inner surface 1b of the wall atthe vessel side to introduce and coat the Ziegler-Natta catalyst on theinner surface 1b of the side wall of the vessel 1, and a catalystcontrol valve 11 for controlling the quantity of the catalyst to beintroduced into the vessel 1 is provided in the conduit 10.

On the other hand, reference numeral 20 designates a rotary transmissionmechanism for rotatably driving the vessel 1 in such a manner that adrive gear 21 rotated by a drive source, not shown, is engaged in meshwith a driven gear 23 provided on the outer periphery of the vessel 1through an intermediate gear 22.

In operation for producing the polyacetylene film by using the apparatusthus constructed as described above, the vessel 1 is evacuated invacuum, the vessel 1 is then rotated by the rotary transmissionmechanism 20, the catalyst control valve 11 is suitably opened to coatthe Ziegler-Natta catalyst dropped from the opening 10a at the end ofthe conduit 10 from the inner surface 1b of the side wall of the vessel1 on the entire surface of the inner surface 1c of the bottom. In thiscase, the control valve 11 controls so that the quantity of adequateamount.

Subsequently, after the catalyst control valve 11 is closed, the gascontrol valve 8 is opened to introduce the acetylene gas into thevessel 1. Thus, the acetylene gas is polymerized by the Ziegler-Nattacatalyst coated on the inner surface 1b of the side wall and the innersurface 1c of the bottom in the vessel to produce the polyacetylene film12. In this case, the vessel 1 may remain rotating or may be stoppedsteadily.

FIGS. 4 and 5 show a second embodiment modified from the firstembodiment of the invention. The vessel 1 is rotatably in the firstembodiment, while the conduit 10 for introducing the catalyst is rotatedin this modified embodiment.

More particularly, reference numeral 20 designates a rotary transmissionmechanism in the same manner as the first embodiment, but, in themodified embodiment, a drive gear rotated by a drive source, not shown,is engaged in mesh with a driven gear 23 provided on the outer peripheryof the conduit 10 through an intermediate gear 22.

The conduit 10 is not merely passed through the cap 4, but is passed inthe sealed state through an O-ring engaged with the opening at the uppersurface of the cap 4.

Further, a mechanical seal 14 is interposed in the jointed sectionbetween the rotary portion 10' and the nonrotary portion 10" of theconduit 10 so that the rotary portion 10' may rotate in the sealedstate.

The conduit 10 in the above embodiments is constructed as describedabove. However, the conduit 10 may also be constructed so that theopening 10a at the end can be adjusted at the position in an elevationaldirection, thereby controlling the area to be coated with the catalystto the inner surface 1b of the side wall and the inner surface 1c of thebottom in the vessel 1 so as to freely select the area of thepolyacetylene film 12 to be produced.

Further, the time required for coating the catalyst may be shortened byproviding a plurality of conduits 10.

A third embodiment of the invention will now be described in detail withreference to FIGS. 6 to 9. The fundamental structure of this embodimentof the invention is the same as that of the first embodiment and thesame reference numerals indicate the same or corresponding parts.

The difference between the third embodiment and the first embodiment ofthe invention resides in that the vessel 1 is not only formed in acylindrical shape but also the bottom 1d of the vessel 1 is tapered tobe converged downwardly, an exit 1f for exhausting the catalyst isformed at the center of the bottom 1d so as to pass through the rotarysupport shaft 1a, the shaft 1a having the exit 1f is further connectedto the catalyst exhaust conduit 14 through a mechanical seal 13, and acatalyst exhaust valve 15 is interposed in the conduit 14 forcontrolling the quantity of the catalyst to be flowed out.

Then, in operation for producing the polyacetylene film with theapparatus thus constructed as described in this embodiment, the vessel1, in which inert gas is sealed, is first rotated by the rotarytransmission mechanism 20, the catalyst control valve 11 is then openedsuitably to coat the Ziegler-Natta catalyst dropped from the opening 10aat the end of the conduit 10 over the entire surfaces of the innersurface 1b of the side wall and the inner surface 1e of the bottom inthe vessel 1. In this case, the apparatus of this embodiment adequatelycontrols the quantity of the catalyst to be introduced by the controlvalve 11 in the same manner as the first embodiment, but the catalystcontrol valve 15 controls to open in the degree as required so that thequantity of the catalyst to be coated does not become excessive. Thefollowing steps of producing the polyacetylene film of the apparatus ofthis embodiment is entirely the same as the content described withrespect to the first embodiment of the invention.

A fourth embodiment is shown in FIGS. 8 and 9 and is constructedcorresponding to the contents of the modification shown in FIGS. 4 and 5with respect to the first embodiment of the invention. The vessel 1 isrotatable in the embodiments shown in FIGS. 6 and 7, while, in themodified embodiment in FIGS. 8 and 9, the catalyst introducing conduit10 is rotatable. Since the construction and the operation of thismodified embodiment is substantially the same as those shown in FIGS. 4and 5, the detailed description of this modified embodiment will beomitted.

According to the first embodiment of the present invention as describedabove, there is provided an apparatus for producing a polyacetylene filmby contacting acetylene gas with Ziegler-Natta catalyst to polymerizethe acetylene gas in a vessel 1 which comprises a catalyst introductionconduit 10 to be introduced with the Ziegler-Natta catalyst provided ata cap 4 provided at the top of the vessel 1 and having an end opening10a disposed in the vicinity of the inner surface 1b of the side wall ofthe vessel in such a manner that the conduit 10 and the vessel 1 arerelatively moved in rotation, and a rotary transmission mechanism 20 fordriving to rotatably coat the catalyst flowing out from the end opening10a of the conduit 10 on the inner surface 1b of the bottom from theinner surface 1b of the side wall of the vessel 1. Thus, thepolyactylene film 12 can be produced in a uniform thickness and in arelatively large area by introducing the Ziegler-Natta catalyst of thesuitable quantity, and the catalyst can be spread over the entiresurface rapidly by the relative rotation between the conduit and thevessel. Accordingly, the catalyst is not partly excessively coated, andthereby a polyacetylene film of high quality is obtained.

Further, according to the third embodiment of the present invention,there is provided an apparatus for producing a polyacetylene film,constructed in the same manner as the first embodiment, in which thebottom of the vessel is further formed in a cconverted tapered shape andan exit 1f if provided at the end of the bottom of the vessel. Thus, thecatalyst is not excessively coated due to the introduction of theexcessive catalyst, thereby obtaining the polyacetylene film of highquality in addition to the advantages of the first embodiment of theinvention.

What is claimed is:
 1. A process for the catalytic film polymerizationof acetylene, comprising the steps of:(a) providing an apparatus whichincludes(1) a polymerization vessel having an interior surface defininga sidewall portion and a bottom portion; (2) means for feeding acatalyst exclusively along said sidewall portion; (3) means forcontaining said catalyst to form a layer thereof along said interiorsurface, said coating means preventing a flow of catalyst from saidsidewall portion to said bottom portion in excess of that necessary toproduce a polymerized film of uniform thickness along said interiorsurface; and (4) means for maintaining a single continuous monomer gasstream at said interior surface sufficient for uniform polymerization atall locations along said interior surface; (b) producing an inertatmosphere in the polymerization vessel and feeding a catalystexclusively along said sidewall portion of said polymerization vessel;(c) coating said catalyst along said interior surface of saidpolymerization vessel and allowing said catalyst to flow from saidsidewall portion to said bottom portion; (d) regulating said catalystflow to maintain a level of flow no greater than that necessary toproduce a polymerized film of uniform thickness in step (f); (e) feedingan acetylene monomer gas to said vessel; (f) maintaining a homogeneousacetylene monomer gas concentration along said interior surface of saidpolymerization vessel; and (g) polymerizing said acetylene monomer gasto form a polymer film of uniform thickness along said interior surface.2. A process according to claim 1, wherein said process includes thestep of removing said catalyst from said bottom portion after it flowsto said bottom portion in step (c).
 3. A process according to claim 1,wherein said coating step includes rotating said polymerization vesselrelative to said catalyst feeding means.
 4. A process according to claim1, wherein said coating step includes rotation said catalyst feedingmeans relative to said polymerization vessel.
 5. A process according toclaim 1, wherein said catalyst comprises a Ziegler-Natta catalyst.